CN109289508B - Preparation method of high-hydrophobicity zeolite material - Google Patents
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- CN109289508B CN109289508B CN201811245142.9A CN201811245142A CN109289508B CN 109289508 B CN109289508 B CN 109289508B CN 201811245142 A CN201811245142 A CN 201811245142A CN 109289508 B CN109289508 B CN 109289508B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/106—Gold
Abstract
The invention discloses a preparation method of a high-hydrophobicity zeolite material, which comprises the following steps: selecting a mixture of ZSM zeolite raw materials and BEA zeolite raw materials, mixing, grinding into powder, adding an auxiliary agent, bonding, and pressing into a block blank; placing the massive blank into a reaction kettle by a hydrothermal method, and carrying out hydrothermal in-situ crystal transformation treatment by adopting water vapor; removing Na and Al by using inorganic acid; soaking in noble metal solution; and (4) carrying out hydrophobic treatment to obtain the high-hydrophobicity zeolite material. The high-hydrophobicity zeolite material overcomes the defects of adsorption and desorption operation of the active carbon on the organic waste gas, can efficiently and selectively absorb the organic waste gas under high humidity, and efficiently desorbs at the high temperature of 150-200 ℃, and has the advantages of greatly improved comprehensive conversion rate, simple process, easily obtained raw materials and extremely high application and popularization values due to the existence of noble metal catalysis.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a preparation method of a high-hydrophobicity zeolite material.
Background
At present, most industrial waste gas discharged by chemical enterprises contains combustible gas such as H2, CO and CH4And the combustible gas contained in the industrial waste gas only accounts for 10-20% of the total amount of the waste gas, so that the heat value of the waste gas is not high, the gas supply pressure is low, and is about 0.4-1.25 Kpa, and the industrial waste gas with low heat value and gas pressure cannot be normally and stably combusted by using a common gas burner at all, so that most of the industrial waste gas is directly discharged into the atmosphere, and resources are wasted and the environment is polluted.
In the prior art, active carbon materials (honeycomb active carbon, granular active carbon and active carbon fiber) are mainly used as an adsorbent, the safety of the active carbon materials is poor when the active carbon materials are regenerated by hot airflow, and when the temperature of the regenerated hot airflow reaches more than 100 ℃, an adsorption bed is easy to catch fire. And hot air flow is adopted to purge and regenerate the activated carbon, because the regeneration temperature is low, partial high-boiling-point compounds cannot be completely desorbed after the desorption period is finished, and the high-boiling-point compounds are accumulated in an activated carbon bed layer to reduce the adsorption capacity of the activated carbon bed layer. Typical regeneration temperatures cannot exceed 120 ℃ due to safety issues. In addition, activated carbon has a strong water absorption capacity, and when the humidity of exhaust gas is high (more than 60%), the purification capacity of organic matters is rapidly reduced.
Therefore, activated carbon has not been able to meet the use of most of the current adsorption media for the discharge of VOCs from chemical industries. The zeolite molecular sieve is a hydrate of crystalline aluminosilicate metal salt with tetrahedral framework structure, the treated zeolite molecular sieve has the structure and characteristics of crystals, the surface is a solid framework, the molecular sieve selectively adsorbs molecules according to the size of holes in the crystals, namely the molecular sieve adsorbs molecules with certain size and repels molecules of larger substances, and the pore diameter of the internal structure of the zeolite in a zeolite runner is close to the particle diameter of most organic waste gas VOCs molecules, so the zeolite molecular sieve is particularly suitable for adsorbing pollution components in organic waste gas. The zeolite in the zeolite runner has hydrophobicity, and can selectively adsorb nonpolar molecules in the organic waste gas according to the size and polarity of the molecules, so that the zeolite runner has better adsorption characteristics on most organic waste gases.
Therefore, it is an urgent problem to develop a zeolite molecular sieve material with good hydrophobicity, which can achieve the purpose of adsorbing organic waste gas under high humidity and desorbing organic waste gas under high temperature.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a preparation method of a high-hydrophobicity zeolite material, which aims to solve the problems in the prior art.
The invention content is as follows: a preparation method of a high-hydrophobicity zeolite material comprises the following steps: (1) selecting ZSM zeolite raw materials in mass ratio: mixing BEA zeolite raw materials with 2-3.5 of mixed zeolite raw materials, grinding the mixture into powder with more than 400 meshes, adding an auxiliary agent, bonding and pressing the powder into a block blank;
(2) placing the massive blank into a reaction kettle by a hydrothermal method, and carrying out hydrothermal in-situ crystal transformation treatment by adopting water vapor at 160-250 ℃ for 12-30 h;
(3) carrying out Na and Al removal treatment on the crystal-transferred massive blank by using inorganic acid, and treating the crystal-transferred massive blank for 20-32 hours at 55-75 ℃ by using sulfuric acid, hydrochloric acid or perchloric acid with the concentration of 0.2-1 mol/L;
(4) soaking the massive blank treated by the inorganic acid into a noble metal solution for soaking for 2-6 h at the temperature of 30-45 ℃, taking out the massive blank until the massive blank is burnt under hydrogen flame to obtain a massive blank loaded with noble metal;
(5) and (3) carrying out hydrophobic treatment on the material in the step (4), wherein the hydrophobic treatment condition is that saturated steam with the temperature of 650-750 ℃ is used for treating for 4-12 h, and slowly cooling to room temperature for not less than 6h to obtain the high-hydrophobicity zeolite material.
Preferably, the ZSM zeolite raw material is a ZSM-5 type zeolite.
Preferably, in the step (1), the ZSM zeolite raw material and the BEA zeolite raw material have the micropore diameter of 0.5-1.5nm and the specific surface area of more than 200m2(ii) in terms of/g. The two zeolite raw material components with the micropore diameter and the specific surface area can ensure the micropore property and the adsorption efficiency of the finished product after treatment.
Furthermore, the molar ratio of silicon to aluminum of the BEA zeolite raw material is 10-200, and the molar ratio of silicon to aluminum of the ZSM zeolite raw material is 60-120. The improvement of the mole ratio of silicon to aluminum is beneficial to playing the effects of adsorbing and catalyzing organic tail gas.
Preferably, the noble metal solution is one of palladium chloride, chloroauric acid or chloroplatinic acid. The medium solution of the noble metal has extremely high catalytic activity and is particularly favorable for being combined with the material of the invention.
Preferably, the mass of the auxiliary agent accounts for 5-12% of the mass of the mixed zeolite raw material, and the auxiliary agent comprises the following components in parts by weight:
compared with the prior art, the invention has the beneficial effects that: the preparation method of the high-hydrophobicity zeolite material provided by the invention is simple in formula, simple in preparation steps, wide in application and particularly suitable for absorption and oxidation operation of organic waste gas. The ZSM and BEA materials are mixed to integrate the structural advantages of the ZSM and BEA materials, so that the component proportion is suitable for the carrier modification foundation for organic waste gas absorption; the method has the advantages that the steps of hydrothermal in-situ crystal transformation, Na and Al removal by inorganic acid, precious metal impregnation and hydrophobization treatment are compact, the material can be endowed with excellent crystal performance, surface performance and catalytic performance, meanwhile, due to the fact that the material is massive, excessive treatment is avoided, the treatment depth is slowed down, the comprehensive performance of the material is self-balanced, and the physical and chemical properties of the material are greatly optimized by adding the auxiliary agent. The high-hydrophobicity zeolite material overcomes the defects of adsorption and desorption operation of the active carbon on the organic waste gas, can efficiently and selectively absorb the organic waste gas under high humidity, and efficiently desorbs at the high temperature of 150-200 ℃, and has the advantages of greatly improved comprehensive conversion rate, simple process, easily obtained raw materials and extremely high application and popularization values due to the existence of noble metal catalysis.
Detailed Description
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following will briefly describe the embodiments.
Examples 1 to 5
A preparation method of a high-hydrophobicity zeolite material comprises the following steps:
(1) selecting ZSM zeolite raw materials in mass ratio: mixing BEA zeolite raw materials with 2-3.5 of mixed zeolite raw materials, grinding the mixture into powder with more than 400 meshes, adding an auxiliary agent, bonding and pressing the powder into a block blank; the ZSM zeolite raw material is preferably ZSM-5 type zeolite, the diameter of micropores of the ZSM zeolite raw material and the BEA zeolite raw material is 0.5-1.5nm, and the specific surface area is more than 200m2The mole ratio of silicon to aluminum of the BEA zeolite raw material is 10-200, and the mole ratio of silicon to aluminum of the ZSM zeolite raw material is 60-120;
(2) placing the massive blank into a reaction kettle by a hydrothermal method, and carrying out hydrothermal in-situ crystal transformation treatment by adopting water vapor at 160-250 ℃ for 12-30 h;
(3) carrying out Na and Al removal treatment on the crystal-transferred massive blank by using inorganic acid, and treating the crystal-transferred massive blank for 20-32 hours at 55-75 ℃ by using sulfuric acid, hydrochloric acid or perchloric acid with the concentration of 0.2-1 mol/L;
(4) soaking the massive blank treated by the inorganic acid into a noble metal solution for soaking for 2-6 h at the temperature of 30-45 ℃, taking out the massive blank until the massive blank is burnt under hydrogen flame to obtain a massive blank loaded with noble metal; the noble metal solution is one of palladium chloride, chloroauric acid or chloroplatinic acid;
(5) and (3) carrying out hydrophobic treatment on the material in the step (4), wherein the hydrophobic treatment condition is that saturated steam with the temperature of 650-750 ℃ is used for treating for 4-12 h, and slowly cooling to room temperature for not less than 6h to obtain the high-hydrophobicity zeolite material.
The mass of the auxiliary agent accounts for 5-12% of the mass of the mixed zeolite raw material, and the auxiliary agent comprises the components in parts by weight shown in the table 1 in the embodiments 1-5.
Components in the examples of Table 1
Wherein the biological glue is one of donkey-hide gelatin, gum, Arabic gum and shellac.
Measuring the absorption rate of the organic waste gas by using a mixture of steam with the saturation of 75-80% and the organic waste gas at the flow rate of 60-200L/min through the zeolite rotating wheel filled with the high-hydrophobicity zeolite material; and (3) introducing air to desorb the zeolite with saturated absorption at 150-175 ℃, converting one part of the zeolite, desorbing the other part of the zeolite to obtain the conversion rate and the desorption rate of the organic waste gas, wherein the sum of the conversion rate and the desorption rate under the same condition is the effective treatment rate, and the data are summarized as shown in table 2.
Table 2 absorption, conversion and desorption rates of the examples
The hydrophobic zeolite material can achieve the purposes of adsorbing organic waste gas under high humidity and efficiently desorbing at high temperature, and has higher total treatment efficiency because part of organic matters are converted by catalytic oxidation.
The above embodiments are only intended to illustrate the preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, various modifications and equivalent substitutions can be made without departing from the principle of the present invention, and the scope of the present invention is still covered by the claims.
Claims (5)
1. A preparation method of a high-hydrophobicity zeolite material is characterized by comprising the following steps:
(1) selecting ZSM zeolite raw materials in mass ratio: mixing BEA zeolite raw materials with 2-3.5 of mixed zeolite raw materials, grinding the mixture into powder with more than 400 meshes, adding an auxiliary agent, bonding and pressing the powder into a block blank;
(2) placing the massive blank into a reaction kettle by a hydrothermal method, and carrying out hydrothermal in-situ crystal transformation treatment by adopting water vapor at 160-250 ℃ for 12-30 h;
(3) carrying out Na and Al removal treatment on the crystal-transferred massive blank by using inorganic acid, and treating the crystal-transferred massive blank for 20-32 hours at 55-75 ℃ by using sulfuric acid, hydrochloric acid or perchloric acid with the concentration of 0.2-1 mol/L;
(4) soaking the massive blank treated by the inorganic acid into a noble metal solution for soaking for 2-6 h at the temperature of 30-45 ℃, taking out the massive blank until the massive blank is burnt under hydrogen flame to obtain a massive blank loaded with noble metal;
(5) carrying out hydrophobic treatment on the material in the step (4), wherein the hydrophobic treatment condition is that saturated steam with the temperature of 650-750 ℃ is used for treating for 4-12 h, slowly cooling to room temperature, and the cooling time is not less than 6h, so as to obtain the high-hydrophobicity zeolite material;
the mass of the auxiliary agent accounts for 5-12% of the mass of the mixed zeolite raw material, and the auxiliary agent comprises the following components in parts by weight:
2. the method of claim 1, wherein the ZSM zeolite is a ZSM-5 type zeolite.
3. The method of claim 1, wherein in step (1), the ZSM zeolite material and BEA zeolite material have a pore diameter of 0.5-1.5nm and a specific surface area of more than 200m 2/g.
4. The method of claim 3, wherein the molar ratio of silica to alumina of the BEA zeolite material is 10-200, and the molar ratio of silica to alumina of the ZSM zeolite material is 60-120.
5. The method of claim 1, wherein the noble metal solution is one of palladium chloride, chloroauric acid, or chloroplatinic acid.
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| CN102366723A (en) * | 2011-10-10 | 2012-03-07 | 浙江师范大学 | Precious metal monolithic catalyst for organic waste gas treatment and manufacturing method thereof |
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| MY136131A (en) * | 2000-09-14 | 2008-08-29 | Boc Group Inc | Adsorbent compositions |
| CA2795522A1 (en) * | 2010-04-08 | 2011-10-13 | Basf Se | Fe-bea/fe-mfi mixed zeolite catalyst and process for treating nox in gas streams using the same |
| CN102872799B (en) * | 2012-10-24 | 2015-01-14 | 涿鹿恩泽催化材料有限公司 | Preparation method of adsorbent for adsorbing and decomposing indoor harmful gas |
| US9802831B2 (en) * | 2014-07-23 | 2017-10-31 | Chevron U.S.A. Inc. | Synthesis of high silica zeolite via interzeolite transformation without OSDAs |
| US9938157B2 (en) * | 2014-07-23 | 2018-04-10 | Chevron U.S.A. Inc. | Interzeolite transformation and metal encapsulation in the absence of an SDA |
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| CN101757889A (en) * | 2010-01-14 | 2010-06-30 | 上海复旭分子筛有限公司 | BEA type binder-free dewatering silica-rich zeolite adsorbent and preparation method thereof |
| CN102366723A (en) * | 2011-10-10 | 2012-03-07 | 浙江师范大学 | Precious metal monolithic catalyst for organic waste gas treatment and manufacturing method thereof |
| CN103801260A (en) * | 2014-02-14 | 2014-05-21 | 上海复榆新材料科技有限公司 | Method for preparing hydrophobic adsorbent from scraped zeolite molecular sieve catalyst |
| WO2018114291A1 (en) * | 2016-12-22 | 2018-06-28 | Haldor Topsøe A/S | A process for the removal of hydrogen chloride and sulfur oxides from a gas stream by absorption |
| CN107583604A (en) * | 2017-11-02 | 2018-01-16 | 景德镇佳奕新材料有限公司 | A kind of hydrophobicity honeycomb-shaped zeolite material and its preparation method and application |
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